Unsaturated polymers containing reactive groups

ABSTRACT

Process for producing polymers with reactive groups wherein a CH CH-containing polymer is reacted with a substituted olefin in the presence of a catalyst of A. A COMPOUND OF A METAL OF GROUPS Vb or VIb of the Periodic Table and B. AN ORGANO COMPOUND OF A METAL OF GROUPS Ia to IVa of the Periodic Table.

United States Patent 1191 Pampus et al.

1451 Sept. 23, 1975 21 Appl. No.: 217.972

[30] Foreign Application Priority Data Jan. 15, 1971 Germany 2101684 52 us. CL... 260/79.3 R; 260/795 NV; 260/807; 260/8078; 260/821; 260/833; 260/85.1;

260/931; 260/947 HA; 260/947 s;

511 Int. Cl. C08f 27/02; C081 27/06; C081 27/08 [58] Field of Search 260/8078. 85.1. 93.1. 260/947 HA. 94.7 S. 94.7 A. 94.7 N. 879. 79.3 R. 79.5

[56] References Cited UNITED STATES PATENTS 3.116.274 12/1963 Boehm ct all 260/949 C 3.129.208 4/1964 Jezl et a1. 260/949 C 3.412.078 11/1969 Hagcmeyer ct ul 260/937 3.453.346 7/1969 Hagemeyer ct al. 260/878 B 3.458.598 7/1969 Craven 260/878 B 3.481.914 12/1969 Holler et a1. 260/878 B 3.649.709 3/1972 Medema ct a1. 260/947 R 3.707.520 12/1972 Pampus et a1. 260/931 3.804.803 4/1974 Streck et a1 260/931 Primary E.\aminerEdwurd J. Smith Attorney. Agent. or Firm-Connolly and Hutz 57 ABSTRACT Process for producing polymers with reactive groups wherein a -CH=CH-containing polymer is reacted with a substituted olefin in the presence of a catalyst of a. a compound of a metal of groups Vb or Vlb of the Periodic Table and b. an organo compound of a metal of groups [a to [V2] of the Periodic Table.

5 Claims, No Drawings UNSATURATED POLYMERS CONTAINING REACTIVE GROUPS Processes for the preparation of polymers with certain end groups are already knownsThe processes previously described are all restricted to the use of a given initiator system so that the microstructure of the polymers produced is predetermined. These processes are also restricted in the number or the chemical constitution of the functional groups which can be introduced. These processes include, for example, the polymerisation of vinyl compounds initiated by a free radical reaction carried out in the presence of carbontetrachloride or carbon tetrabromide and the reaction of living polymers with compounds which are capable of reacting with an alkali metal-carbon bond.

'It is therefore an object of this invention to introduce any number of reactive groups of various chemical constitution int'o polymers which contain CH=CH- groups. In this process, the introduction of functional groups may be carried out completely independently of the initiator system used for producing the polymer whichcontains --CH=CH-groups and therefore independently of the microstructure of the polymer.

The process of the invention comprises reacting polymers which contain -CH=CH-groups in their main chain and/or in a side chain with substituted olefines of the formula alkaryl, alkoxyalkyl, aroxyalkyl, alkylene carboxyalkyl, 1

alkylene carboxyaryl, alkylcarboxyalkylene, aroxyalkylene, alkylenearylsulphone or alkylenearyl thioether, at

least one of the radicals R is not hydrogen and is substiwhich is substituted by X, preferably on the carbon atom marked with X is preferably chlorine, bromine, iodine, C E N, N0 or The following are examples of such compounds: Allyl chloride, allyl bromide, allyl iodide, crotyl bromide, 1,4-dichlorobutene-2, allyl glycidyl ether, dihydromuconicacid dinitrile, 4,4-dinitrostilbene, an allyl ester of monochloroacetic acid, an allyl ester of o, m, pnitrobenzoic acid, butene-2-dio1-l,4-dich1oroacetate, butene-Z-diol-l,4-di-p-nitrobenzoate, butylene glycol- 1,4-di-p-nitrophenylether, p-nitrocinnamic acid ester, dihydromuconic acid diglycidiyl ester, 1,8- dibromooctene-4, 1-bromo-butene-3, 1 ,4-bis-(pnitrophenyl)-butene-2.

The quantity of the substituted olefin of formula 1 with which the CH=CH-containing polymer is reacted is 0.005 to 0.5 mol per mol of double bonds in the main chain of the polymer, and 0.01 to 1 mol per mol of double bonds in the side chains of the polymer.

Any polymer having CH=CH-groups is suitable in the process of this invention. These -CH=CH-groups can be present in the main chain of the polymer or in side chains or in both.

One suitable class of polymers of this type are those of conjugated dienes having 4 to 8 carbon atoms. This term is understood to include homopolymers, copolymers of different conjugated dienes and copolymers of dienes with up to by weight of monoethylenically unsaturated compounds. Examples of suitable conjugated dienes are 1,3-dienes, such as butadiene, isoprene and piperylene. Their homoand copolymers are suitable regardless of the stearic arrangement of the monomer units and regardless of the relative amount of such dienes in the copolymer.

Examples of monoethylenically unsaturated compounds are aliphatic monovinyl compounds and monovinyl aromatic compounds, such as alkyl esters (preferably 1 to 6 carbon atoms) amides and nitriles of acrylic and methacrylic acid e.g. ethyl acr-ylate, methyl methacrylate, acrylonitrile and methacryl amide and respectively styrene, a-methyl styrene, vinyl toluene and vinyl pyrrolidone.

Examples of this type of polymers are: cis-1,4- polybutadiene, 1 ,2-polybutadiene, cis-l ,4- polyisoprene, 1,2-polyisoprene, all interpolymers of butadiene, isoprene and piperylene, butadiene styrene copolymers wherein the butadiene units have 1,4, 1,2

5 QiG" bonds are .terminal,

or both configurations wherein the distribution of butadiene and styrene units is statistical or block and the weight ratio of butadienezstyrene is 95:5 to 20:80.

Another suitable group of polymers are ethylene,- propylene terpolymers wherein the weight ratio of ethylenezpropylene is 20:80 to 80:20 and which contain l to 20 by weight, preferably 4 to 12 by weight (based on the total polymer) of a polymerisedthird monomer which introduces a -CH=CH-group. Suitable third monomers are conjugated diolefins having 4 to 8 carbon atoms such as butadien'e, isoprene and piperylene and non-conjugated diolefins. Examples of such non-conjugated diolefins are straight or branched chain diolefins such as those in which both double as in 1,4-pentadiene, 1,5-

hexadiene, 2-methyll ,S-hexadiene, 3 ,3-dimethyl-1 ,5-

hexadiene, l,7-octadiene, 1,9-decadiene and 1,19-

icosadiene; diolefins in which only one double bond is terminal, such as l,4-hexadiene, 1,9-octadecadiene, 6-methyl-l ,S-heptadiene, 7-methyll ,6-octadiene and ll-ethyl-l-l l-tridecadiene. Another suitable group of third monomers are those cyclic diolefins which contain a bridged ring and which have 7 to 10 carbon atoms. The bridge is preferably a methano or an ethano-bridge. Examples are unsaturated derivatives of bicyclo(22l)heptane containing 2 double bonds such as bicyclo (221 )hepta-2,5-diene, dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene; unsaturated derivatives of bicyclo-222-octane containing two double bonds such as bicyclo-222-octa-2,5-diene; unsaturated derivatives of bicyclo-32l-octane containing two double bonds, unsaturated derivatives of bicyclo- 33l-nonane containing two double bonds and unsaturated derivatives of bicyclo-322-nonane containing two double bonds. Also suitable are those bicycloolefins which contain an exocyclic double bond; Examples being methylene norbornene and ethylidene norbornene.

Still another group of suitable polymers are cisor transpolyalkenamers. These polymers are obtained by ring opening polymerisation of cyclic monoolefins having 5 to 12 carbon atoms. Most suitable are cisand trans-polypentenamers.

Catalysts consisting of (a) compounds of metals of groups Vb and Vlb of the Periodic System and (b) organometallic compounds of groups la to IVa of the Periodic System are suitable for the process.

The preferred catalysts consist of (a) halides and oxyhalides of tantalum, molybdenum or tungsten, halide meaning fluoride, chloride, bromide and iodide, such as Tac'1j,, TaOCl TaBr MoCl MoOCl WCl WOCI WCI WF WBr WJ,, and (b) organo aluminum or organo tin compounds.

Suitable organo aluminum compounds correspond to the formula wherein R is alkyl or alkoxy having l 1 2 carbon atoms R and R is hydrogen, alkyl or alkoxy having 1-1 2 carbon atoms, halogen (such as F, Cl, Br, l)

Examples of such compounds are:

Preferred is the combination of a tungsten halide (chloride or bromide) and an alkyl aluminum halide (chloride, bromide, iodide).

Suitable organo tin compounds are those of the formula wherein X is hydrogen or halogen such as fluorine, chlorine, bromine and iodine, R is alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms, cycloalkyl having 3 to 8 carbon atoms or alkaryl (combined from alkyl and aryl as defined above) and n is 0, l, 2 or 3. 1

Examples of such compounds are: tin tetramethyl, diethyl dimethyl tin, tetraethyl tin, dibutyl diethyl tin, tetrabutyl tin, tetraisocumyl tin, tetraphenyl tin, triethyl tin fluoride, triethyl tin chloride, triethyl tin bromide, triethyl tin iodide, diethyl tin difluoride, diethyl tin dichloride, diethyl tin dibromide, diethyl tin.diiodide, ethyl tin trifluoride, ethyl tin trichloride, ethyl tin tribromide, ethyl tin triiodide. Tungsten halides (e.g. chloride) and alkyl aluminum halides are especially preferred as catalyst components. The catalyst activity may be increased by the addi-. tion' of co-catalysts (c). The following co-catalysts may be used:

l. Epoxides of the following general formula Z H, alkyl having 1-6 carbon atoms, aryl having 6-20 carbon atoms or aralkyl (combined from alkyl and aryl as defined). Y= H, alkyl having 1+6 carbon atoms, aryl having 6-20 carbon atoms, aralkyl or CH l-lal (Hal F, Cl, Br or I) Z and Y may be substituted e.g. by alkyl (CH and/or halogen (Cl);

2. Acetals of the following general formula:

' in which R represents hydrogen or optionally halogearyl radical and R represents an alk ylaryl radical (alkyl C -C aryl C -C which is optionally substituted with halogen (F, Cl, Br or I); i

3. haloalcohols of the following general formula in which Hal F, Cl, Br or I and R and R, may be the same or different and represent hydrogen or an alkyl, isoalkyl, aryl or aralkyl radical, and R and R may be identical or different and represent fluorine, chlorine,

bromine, iodine, hydrogen, alkyl, aryl or aralkyl; and R and R together with the carbon atom to which they are attached may form a 5 to S-membered carbocyclic ring (alkyl is alkyl having 1-6 carbon atoms, aryl having 6-20 carbon atoms, aralkyl is a combination of both.

4. halophenols of the following general formula wherein W fluorine, chlorine, bromine or iodine and R H, alkyl (C -C aryl (C -(1 alkylaryl (alkyl C -C aryl C C or a condensed cycloaliphatic or aromatic ring.

The following are specific examples of these cocatalysts: ethylene oxide, propylene oxide, epichlorohydrin, I 2-chloroethanol, 2-bromoethanol, 2- fluoroethanol, 2-iodoethanol, 2-chlorocyclohexanol, 2-chlorocyclopentanol, m-, and p-chlorophenol,

di-2-chloro'ethylformal and diethylformal.

The molar ratio of the catalyst components a:b and we is between 1:05 and 1:15 and between 1:03 and zene.

The process according to the invention is generally carried out as follows:

The reaction is usually carried out in an inert solvent but may also be carried out without solvent. The hydrocarbon polymer which contains -CH=CH-groups is generally used in the form of a 5-50% solution. If the polymer with C-H=Cl-l-groups has a low molecular weight (e.g. molecular weights between 2000 and 10,000) the inert solvent may be omitted. The metal compound (a) of the catalyst is added to the polymer solution, followed by the substituted olefin of formula This mixture is heated to the required reaction temperature which is between C and +60C and preferably between 20C and +20C.

Lastly, the catalyst is activated by the addition of the organometallic compound (b). The reaction proceeds without substantial evolution of heat and is completed within a period of between 5 minutes and 2 hours.

The sequence in which the reactants and catalyst components are added is not critical but it is advantageous to add the organometallic compound last.

The process according to the invention gives rise to polymers with --CH=CH-groups which contain functional groups. If the --CH=CH-groups are in the main chain in the polymer used as starting material then a reduction in the molecular weight of this polymer takes place at the same time. A rearrangementof cis double bonds to trans double bonds is also observed.

The functionalgroups introduced in this way may be varied by known reactions, for example nitro groups may be reduced to amino groups by known methods: halogens may be substituted by nucleophilic reagents such as amines or mercaptans.

The modified unsaturated polymers obtained by the process of this invention are solid rubber-like products when they have a molecular weight in excess of about 5000 andviscous liquids at lower molecular weights e.g. below 3000. The solid rubber-like products can be used in any application of synthetic rubbers such as in the production of technical rubber articles e.g. rubber hose, conveyor belts, fittings and so on.

They can be vulcanised by the methods usual for rubber, s uch as by means of sulphur and accelerators. The usual rubber additives such as carbon black fillers, pigment stabilizers, extending oils can be added.

When the reactive end groups in the polymers are halogen atoms e.g. chlorine, bromine or iodine, these products can be crosslinked by means of oxides of polyvalent metals such as magnesium oxide by the same procedure used in crosslinking polychloroprene.

When the reactive end groups are nitro groups, they may be reduced to amino groups by catalytic reduction with hydrogen or by means of iron and hydrochloric acid, following art recognized procedures. The thus formed amino groups are reactive with dior polyfunctional carboxylic acid anhydrides such as phthalic anhydride pyrromelytic acid anhydride to form polyimide or polyamide bonds, thus effecting crosslinking. These reactions and their conditions are well-known in the art. Also a reaction of the amino group with a polyisocyanate can be carried out which results in high molecular weight polyureas. This reaction i.e. the reaction of a polyamine and a polyisocyanate is well-known and customary in the polyisocyanate polyaddition art. The amino groups can also react with polyfunctional aromatic or aliphatic carboxylic acid chlorides (e.g. phthalic acid chloride, terephthalic acid chloride, benzene tricarboxylic acid chloride). This reaction leads to same as mentioned above.

Products containing epoxy end groups are crosslinked on addition of polyfunctional carboxylic acids, their anhydrides or of polyfunctional polyamines under conditions well-known from the art of making epoxy resins.

All these methods are alternative to the usual sulphur/accelerator vulcanisation and are applicable to all polymers of this invention including liquid products. The result of these crosslinking reactions is'a rubberlike crosslinked polymer in all instances. The crosslinking methods mentioned above which are in principle art recognized offer decisive advantages over the usual sulphur accelerator vulcanisation as the crosslinking density (i.e. number of crosslinks per unit of volume) can'be predetermined. When there are reactive groups only in terminal position of the polymer molecule, the crosslinking density is directly proportional to the molecular weight of the product. Thus it is determined by the molecular weight of the polymer and low molecular weight polymers yield high crosslinking density and high molecular weight polymers yield low crosslinking density.

When the reactive groups are in side-chains the crosslinking density is directly proportional to their number. As this number is known from the structure of the polymer, the crosslinking density can also be predetermined.

The crosslinkedproducts have the same applications as rubber crosslinked by the usual sulphur/accelerator vulcanisation. They are suitable for producing any shaped rubber article, such as those mentioned above.

' EXAMPLE 1 A solution in toluene of the reaction product of WCI and 2 mols of epichlorohydrin are added to a solution of 50 g of cis-1,4-polybutadiene having 95% of cis double bonds in 1 l of toluene with exclusion of air and moisture at C, the amount of tungsten being such that 1 l of polymer solution contains 1.0 mmol of tungsten. g,of crotyl bromide are then added and lastly 4 mmol of diethyl aluminium chloride. The polymer solution is stirred for 2 hours at 0C to+5C and the polymer is then precipitated with alcohol. When the polymer has been purified by reprecipitation, 75% of the double bonds have th trans configuration and the polymer is found on analysis to have a bromine content of about 7.4%. p I

EXAMPLE 2 a low molecular weight modified polybutadiene having .a chlorine content of 62% are obat ined.

EXAMPLE 3 2 g of dihydromuconic acid dinitrile are added to a solution of 50 g of cis-polybutadiene in l l of toluene. 2.0 mmol of the reaction product of WCI and epichlorohydrin (molar ratio 1:2) are then added at +10C, followed by 8.0 millimols of diethylaluminium chloride. After a reaction time of 5 hours, the modified p01- ymer is precipitated and is then reprecipitated for the purpose of analysis. The nitrogen content is 1.1%.

EXAMPLE 4 I 4.0 mmol of the tungsten compound described in Example 3 are added to a solution of 50 g of transpolypentenamer rubber in 1 liter of toluene. The temperature of the solution is then adjusted to 10C. 10 g of 1,4-dichlorobutene-2 are added to the solution immediately after the addition of 16.0 mmol of aluminium diethyl chloride. The viscosity of the solution has dropped considerably after a reaction time of 4 hours.

'5 g of K CO and 20 m1 of methanol are added to the solution. The precipitate is left to settle and the clear solution is concentrated by evaporation under vacuum to 150 ml and then precipitated with methanol. The oily polymer is found on analysis to have a chlorine content of 5.3%.

EXAMPLE 5 A solution of 50 g of polybutadiene in l l of toluene is cooled to +5C and 2.0 millimol of the reaction product of WCl and epichlorohydrin (molar ratio 1:2) are added. The reaction mixture is then cooled to 20C. 8.0 mmol of aluminium triethyl are added,'follow'ed immediately by 10 g of allyl glycidyl ether. The temperature is allowed to rise first to 0C and then after thereaction time of one hour to +25C. The modified polymer was precipitated with ethanol after 15 hours and carefully dried under vacuum. Analysis of the polymer indicated 0.8% of oxygen.

EXAMPLE 6 g of butadiene are polymerised in 1.0 l of benzene as solvent with the aid of 0.05 mmol of cobalt octoate and 5.0 millimol of ethyl aluminium sesquichloride. After a polymerisation time of 4 hours at 50C, 8.0 mmol of diethyl aluminium chloride were added to the resulting polybutadiene solution. 20 g of 1,4- dichloro-butene-2 were then added at +10C. After the addition of 2.0 mmol of the reaction product of WC], and'epichlorohydrin, the reaction mixture was left to stand for 12 hours at'20C. On working up the product,

a modified polybutadiene having a chlorine content of l 5.8% was obtained.

We claim:

1. A process for introducing reactive chlorine, bro- I 0.0l to l mol of said olefin per mol of double bonds in the side chains of said polymer, said olefin being of the and said reaction being carried out in the presence of formula an organometallic mixed catalyst of a. a halideof a metal of Group Vb or Vlb of the Peri- R CH CH R odic System, wherein R is hydrogen, alkyl having 1 to 6 carbon b. an organometallic compound of Groups la and IV atoms, cycloalkyl having 5 to 7 carbon atoms, of the Periodic System and c. a cocatalyst selected from the group consisting of l. a compound of the formula wherein Z is hydrogen, alkyl having 1 to 6 carbon x Q atoms, aryl having 6 to carbon atoms, aralkyl having 6 to 20 carbon atoms in the aryl moiety and l to 6 carbon atoms in the alkyl moiety or said aryl or aralkyl X substituted with methyl or chlorine and Y is hydrogen,

moiety, -CH Hal wherein Hal is fluorine, chlorine, bromine or iodine or said aryl or aralkyl substituted X with methyl or chlorine and 2. a compound of the formula -CH,-SO,- X l R,--CC|-R,

CH Hal XCH,S-- or x wherein Hal is fluorine, chlorine, bromine or iodine, R and R which may be the same or different are hydro- X gen, alkyl having 1 to 6 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 6 to 20 carbon atoms in the aryl moiety and l to 6 carbon atoms in the alkyl moiety and R and R;, which may be the same or different, are fluorine, chlorine, bromine, iodine, hy-

drogen, alkyl having 1 to 6 carbon atoms, aryl having 6 to 20 carbon atoms or aralkyl having 6 to 20 carbon atoms in the aryl moiety and l to 6 carbon atoms in the alkyl moiety and R, and R when taken together with wherein X is chlorine, bromine, iodine, cyanide, nitro the carbon atoms to which they are attached, form a 5- or to 8-membered carbocyclic ring, the molar ratio of (a):(b):(c) being 1:05 to 15:0.3 to 10.

2. Process according to claim 1 wherein the polymer is a homopolymer of a conjugated diene or a copolymer 0 of a diene with up to 80% by weight of a monoethylenically unsaturated compound. and wherein at least one R is not hydrogen and is sub- 3. Process according to claim 1 wherein the polymer stituted by chlorine, bromine, iodine, cyanide, nitro or is an ethylenepropylene-diolefin-terpolymer.

4. Process according to claim 1 wherein the polymer is a polyalkenamer. 5. Process according to claim 1 wherein the organometallic compound is an aluminum or tin compound.

X 7 20 alkyl having 1 to 6 carbon atoms, aryl having 6 to 20 carbon atoms, aralkyl having 6 to 20 carbon atoms in 2 2 the aryl moiety and l to 6 carbon atoms in the alkyl 

1. A PROCESS FOR INTRODUCING REACTIVE CHLORINE, BROMINE, IODINE, CYANIDE, NITRO OR EPOXY GROUPS INTO A POLYMER CONTAINING -CH=CH-GROUPS SELECTED FROM THE GROUP CONSISTING OF POLYMERS OF CONJUGATED DIENES, SAID DIENES HAVING 4 TO 8 CARBON ATOMS, ETHYLEN-PROPYLENE-DIOLEFIN-RERPOLYMERS AND CIS- AND TRANS-POLYALKENAMERS OBTAINED BY RING OPENING POLYMERIZATION OF CYCLIC MONO-OLEFINS HAVING 5 TO 12 CARBON ATOMS WHICH COMPRISES REACTING AT LEAST ONE SUCH POLYMER WITH AN OLEFIN IN AN AMOUNT OF 0.005 TO 0.5 MOL OF SAID OLEFIN PER MOL OF DOUBLE BONDS IN THE MAIN CHAIN OF SAID POLYMER OF 0.01 TO 1 MOLE OF SAID OLEFIN PER MOL OF DOUBLE BONDS IN THE SIDE CHAINS OF SAID POLYMER, SAID OLEFIN BEING OF THE FORMULA
 1. A COMPOUND OF THE FORMULA
 2. A COMPOUND OF THE FORMULA
 2. Process according to claim 1 wherein the polymer is a homopolymer of a conjugated diene or a copolymer of a diene with up to 80% by weight of a monoethylenically unsaturated compound.
 2. a compound of the formula
 3. Process according to claim 1 wherein the polymer is an ethylenepropylene-diolefin-terpolymer.
 4. Process according to claim 1 wherein the polymer is a polyalkenamer.
 5. Process according to claim 1 wherein the organometallic compound is an aluminum or tin compound. 